Cluster Expansion of Luminescent Digold(I) and Disilver(I) Phosphine-Phosphide Oxide Complexes

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Deprotonation of a diphosphine-secondary phosphine oxide ligand ( o -Ph 2 PC 6 H 4 ) 2 P(O)H (H P 3 O ) affords disilver(I) and digold(I) complexes [M 2 ( P 3 O ) 2 ], M = Ag ( 1 ) and Au ( 2 ). These compounds readily add coordinatively unsaturated AuX fragments (X = C 6 F 5, SPh) by means of metallophilic interactions supported by bridging ligands. The extension of the metal core produces a series of penta- to octanuclear clusters [{M 2 ( P 3 O ) 2 }(AuX) n ] 3 – 7 ( n = 3–6), the structures of which depend on the X group, the nature of the constituting metals, and P = O···HR hydrogen bonding. The newly synthesized clusters demonstrate moderate to intense luminescence as microcrystalline powders, predominantly originating from the triplet excited state and covering a range of wavelengths from 517 to 585 nm. Complexes 3 – 5 containing perfluorophenyl ligands exhibit high photoemission quantum yields under ambient conditions of up to 0.76 in combination with a relatively short lifetime of 0.98 μs for the pentagold cluster [Au 2 ( P 3 O ) 2 (AuC 6 F 5 ) 3 ] ( 4 ). The results illustrate a feasible approach for the preparation of nonionic d 10 coinage metal bright luminophores, derived from a hybrid P{OP – }P scaffold.